Decarboxylative ipso Amination of Activated Benzoic Acids
Decarboxylative ipso Amination of Activated Benzoic Acids
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DOI：
10.1002/anie.201812068
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发表时间：
2019-01-14
影响因子：
16.6
通讯作者：
Goossen, Lukas J.
中科院分区：
文献类型：
--
作者：
Drapeau, Martin Pichette;Bahri, Janet;Goossen, Lukas J.
在以邻菲咯啉为配体，空气或N-甲基吗啉N-氧化物为氧化剂的Pd/Cu体系中，缺电子苯甲酸与未保护胺发生氧化脱羧偶联反应.这种操作简单的苯胺合成法可广泛应用于胺，即使在数克规模上也能得到良好的产率。该反应与其他Pd催化的交叉偶联的正交性允许通过连续的C-C、C-Cl和C-N官能化来简洁地合成多取代芳烃。机制的调查表明，一个高价钯物种的中间。
In the presence of a bimetallic Pd/Cu system with 1,10-phenanthroline as the ligand and either air or N-methylmorpholine N-oxide as the oxidant, electron-deficient benzoic acids undergo oxidative decarboxylative coupling with unprotected amines. This operationally simple aniline synthesis is widely applicable with respect to the amine and gives good yields, even on multigram scale. The orthogonality of this reaction to other Pd-catalyzed cross-couplings allows the concise synthesis of multisubstituted arenes by sequential C-C, C-Cl, and C-N functionalizations. Mechanistic investigations suggest the intermediacy of a hypervalent Pd species.